Photovoltaic device

ABSTRACT

An apparatus includes a substrate; and a photoactive layer disposed on the substrate. The photoactive layer includes an electron acceptor material; an electron donor material; and a material having dipoles.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of and claims priority to U.S. patentapplication Ser. No. 13/707,091, filed on Dec. 6, 2012, which claimspriority under 35 USC §119(e) to U.S. Patent Application Ser. No.61/567,200, filed on Dec. 6, 2011. The entire contents of the aboveapplications are hereby incorporated by reference.

STATEMENT AS TO FEDERALLY SPONSORED RESEARCH

This invention was made with government support under contractHDTRA1-10-1-0098 awarded by the Defense Threat Reduction Agency andunder contract DMR-0820521 awarded by the NSF MRSEC Program. Thegovernment has certain rights in the invention.

BACKGROUND

Organic photovoltaic devices are attractive candidates for energyapplications because of their light weight, flexibility, low cost, andcompatibility with large scale production. The thermodynamic efficiencylimit of organic photovoltaic devices is about 22-27%, which meets orexceeds the efficiency of silicon solar cells and other thin filmphotovoltaic technologies.

SUMMARY

An organic semiconductor photovoltaic device having an enhanced powerconversion efficiency includes a photoactive layer. The photoactivelayer includes a donor layer and an acceptor layer, each formed of anorganic semiconductor. A dipole layer is disposed between the donorlayer and the acceptor layer. The dipole layer is polarizable under anapplied electric field and causes the energy levels of the donor layer,the acceptor layer, or both, to shift. This shift in energy levelsincreases the open circuit voltage across the photovoltaic device,resulting in an improved power conversion efficiency of the device.

In a general aspect, an apparatus includes a substrate; and aphotoactive layer disposed on the substrate. The photoactive layerincludes an electron acceptor material; an electron donor material; anda material having dipoles.

Embodiments may include one or more of the following.

The photoactive layer includes an acceptor layer formed of the electronacceptor material; a donor layer formed of the electron donor material;and a dipole layer formed of the material having dipoles and disposedbetween the acceptor layer and the donor layer. In some cases, thedipole layer is less than 1 nm thick. In some cases, the dipole layer isa monomolecular layer.

The photoactive layer is a single layer that includes the electronacceptor material, the electron donor material, and the polarizablematerial.

The electron acceptor material includes fullerenes.

The dipoles align upon application of a bias electric field.

The material having dipoles has a polarization charge density of atleast about 5 mC/m².

The material having dipoles is configured to cause a shift in an energylevel of at least one of the electron acceptor material and the electrondonor material. In some cases, the dipoles reduce an offset between thelowest unoccupied molecular orbits of the electron acceptor material andthe electron donor material.

The material having dipoles includes a ferroelectric polymer. In somecases, the material having dipoles includes polyvinylidene fluoride andtetrafluoroethylene.

The material having dipoles includes liquid crystal molecules.

At least one of the electron acceptor material and the electron donormaterial includes an organic semiconductor material.

In a general aspect, an apparatus includes an electrically conductivesubstrate; and a photoactive layer disposed on the substrate. Thephotoactive layer includes an electron acceptor material; an electrondonor material; and a material having dipoles; and an electrical contactdisposed on the photoactive layer.

Embodiments may include one or more of the following.

The photoactive layer includes an acceptor layer formed of the electronacceptor material; a donor layer formed of the electron donor material;and a dipole layer formed of the material having dipoles and disposedbetween the acceptor layer and the donor layer.

The photoactive layer is a single layer that includes the electronacceptor material, the electron donor material, and the material havingdipoles.

The material having dipoles is configured to increase an open circuitvoltage between the substrate and the electrical contact.

The material having dipoles is configured to cause a shift in an energylevel of at least one of the electron acceptor material and the electrondonor material

The dipoles align upon application of a bias to the polarizablematerial.

The substrate is transparent.

At least one of the electron acceptor material and the electron donormaterial comprises an organic semiconductor material.

In a general aspect, a method includes forming a photoactive layer on anelectrically conductive substrate. The photoactive layer includes anelectron acceptor material; an electron donor material; and a materialhaving dipoles. The method further includes forming an electricalcontact on the photoactive layer; and applying an electrical bias to thematerial having dipoles.

Embodiments may include one or more of the following.

Forming the photoactive layer includes forming an acceptor layerincluding the electron acceptor material; forming a donor layerincluding the electron donor material; and forming a dipole layerincluding the material having dipoles between the acceptor layer and thedonor layer.

Forming the photoactive layer comprises forming a single layer thatincludes the electron acceptor material, the electron donor material,and the material having dipoles.

Applying an electrical bias to the material having dipoles includescausing dipoles to align.

Applying an electrical bias to the material having dipoles includescausing an increase in an open circuit voltage between the substrate andthe electrical contact.

At least one of the electron acceptor material and the electron donormaterial is an organic semiconductor material.

The techniques described herein may have one or more of the followingadvantages. For instance, the open circuit voltage of an organicphotovoltaic device can be increased by inserting a dipole layer thattunes the energy level offset of the donor semiconductor material andthe acceptor semiconductor material in the device. This tuning of energylevels can be achieved without altering the chemical structure of thedonor and acceptor materials, thus allowing donor and acceptor materialsto be selected based on desired characteristics such as stability, bandgap, mobility, or other characteristics.

Other features and advantages are apparent from the followingdescription and from the claims.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a diagram of a photovoltaic device.

FIG. 2 is a schematic diagram of the molecular structure of a dipolelayer.

FIG. 3 is a flowchart of a process for making a photovoltaic device.

FIGS. 4A and 4B are energy level diagrams of a semiconductorheterostructure without and with a dipole layer, respectively.

FIG. 5 is a plot of photoluminescence intensity.

FIG. 6 is a plot of current density versus voltage.

FIG. 7 is a plot of dark current of a photovoltaic device.

FIGS. 8A and 8B are piezoresponse force microscopy amplitude and phaseimages, respectively. The image size is 1 μm×1 μm.

FIG. 9A is a piezoresponse force microscopy topography image of ananoisland.

FIG. 9B is a plot of piezoresponse force microscopy phase and amplitudehysteresis loops.

FIGS. 9C and 9D are piezoresponse force microscopy phase images of ananoisland before and after application of a reverse bias, respectively.

FIGS. 10A and 10B are PFM topography and surface potential images,respectively.

FIG. 10C is a cross-sectional profile of the surface potential image ofFIG. 10B.

FIG. 11 is a diagram of a proposed mechanism for the origin of thepotential difference shown in FIG. 10C.

FIG. 12 is a diagram of a photovoltaic device.

FIG. 13A is a plot of current density versus voltage for thephotovoltaic device of FIG. 12.

FIG. 13B is a table of performance parameters.

DETAILED DESCRIPTION

Referring to FIG. 1, an organic semiconductor photovoltaic device 100having an enhanced power conversion efficiency includes a photoactivelayer 102. The photoactive layer 102 includes a donor layer 114 and anacceptor layer 116, each formed of an organic semiconductor. The donorlayer 114 includes an electron donor material, and the acceptor layer116 includes an electron acceptor material. A dipole layer 118 isdisposed between the donor layer 114 and the acceptor layer 116. Thedipole layer 118 is polarizable under an applied electric field andcauses the energy levels of the donor layer 114, the acceptor layer 116,or both, to shift. This shift in energy levels increases the opencircuit voltage across the photovoltaic device 100, resulting in animproved power conversion efficiency of the device.

The donor layer 114 and the acceptor layer 116 are formed of organicsemiconductor materials. In the examples described herein, the donorlayer 114 and the acceptor layer 116 are formed ofpoly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid (PC₆₀BM,referred to herein as PCBM), respectively. Other organic semiconductormaterials may also be used to form the donor layer 114 and the acceptorlayer 116, some examples of which are listed below.

The donor layer 114 may be formed of any appropriate p-type organicsemiconductor material or combination of materials. For example, thedonor layer may be formed of one or more of the following materials: aphthalocyanine complex, a porphyrin complex, a polythiophene (PT) orderivatives thereof, a polycarbazole or derivatives thereof, apoly(p-phenylene vinylene) (PPV) or derivatives thereof, a polyfluorene(PF) or derivatives thereof, a cyclopentadithiophene-based polymer, abenzodithiophene (BDT)-based polymer, and combinations thereof. Forinstance, polythiophenes and derivatives thereof, polycarbazoles andderivatives thereof, and phthalocyanine complexes can be used to formthe donor layer 114. More specifically, the following materials can beused as electron donor materials: subphthalocyanine (SubPC), copperphthalocyanine (CuPc), Zinc phthalocyanine (ZnPc),poly(3-hexylthiophene) (P3HT), poly(3-octylthiophene) (P3OT),poly(3-hexyloxythiophene) (P3DOT), poly(3-methylthiophene) (PMeT),poly(3-dodecylthiophene) (P3DDT), poly(3-dodecylthienylenevinylene)(PDDTV), poly(3,3 dialkylquarterthiophene) (PQT),poly-dioctyl-fluorene-co-bithiophene (F8T2),Poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-bldithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]](PTB7), poly-(2,5,-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene)(PBTTT-C12),poly[2,7-(9,9′-dihexylfluorene)-alt-2,3-dimethyl-5,7-dithien-2-yl-2,1,3-benzothiadiazole](PFDDTBT),poly{[2,7-(9,9-bis-(2-ethylhexyl)-fluorene)]-alt-[5,5-(4,7-di-20-thienyl-2,1,3-benzothiadiazole)]}(BisEH-PFDTBT),poly{[2,7-(9,9-bis-(3,7-dimethyl-octyl)-fluorene)]-alt-[5,5-(4,7-di-20-thienyl-2,1,3-benzothiadiazole)]}(BisDMO-PFDTBT),poly[N-9″-hepta-decanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)](PCDTBT),poly[4,8-bis-substituted-benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl-alt-4-substituted-thieno[3,4-b]thio-phene-2,6-diyl](PBDTTT-C-T),Poly(benzo[1,2-b:4,5-b′]dithiophene-alt-thieno[3,4-c]pyrrole-4,6-dione(PBDTTPD),poly((4,4-dioctyldithieno(3,2-b:2′,3′-d)silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl)(PSBTBT), and combinations thereof.

The acceptor layer 116 may be formed of any appropriate n-type organicsemiconductor material or combination of materials. For examples, theacceptor layer 116 may be formed of one or more of the followingmaterials: a fullerene or derivatives thereof, a perylene derivative, a2,7-dicyclohexyl benzo[lmn][3,8]phenanthroline derivative, a1,4-diketo-3,6-dithienylpyrrolo[3,4-c]pyrrole (DPP) derivative, atetracyanoquinodimethane (TCNQ) derivative, a poly(p-pyridyl vinylene)(PPyV) derivative, a 9,9′-bifluorenylidene (99BF) derivative, abenzothiadiazole (BT) derivative, and combinations thereof. Forinstance, fullerenes and derivatives thereof can be used to form theacceptor layer 116. More specifically, the following materials can beused as electron acceptor materials: [6,6]-phenyl-C61-butyric acid(PC₆₀BM, referred to herein as PCBM),[6,6]-(4-fluoro-phenyl)-C₆₁-butyric acid methyl ester (FPCBM),[6,6]-phenyl-C71 butyric acid methyl ester (PC₇₀BM), indene-C60bisadduct (IC₆₀BA), indene-C70 bisadduct (IC₇₀BA), fullerene-C60,fullerene-C70, carbon nanotubes (CNT), a carbon onion, and combinationsthereof.

The dipole layer 118 is generally formed of a material that has dipolesand that has a high polarization charge density, such as at least about5 mC/m². The dipole layer is sufficiently thin so as not to adverselyaffect the efficiency of photoinduced charge transfer between the donorlayer 114 and the acceptor layer 116 but thick enough to be able toretain its polarization. For instance, the dipole layer may be, e.g., 1nm thick, 0.6 nm thick, or the thickness of a monomolecular layer of thematerial of the dipole layer. The dipole layer may be, e.g., aferroelectric block copolymer, a liquid crystal, or another materialthat has dipoles and that can retain its polarization.

In one example, the dipole layer 118 is formed of a ferroelectricpolyvinylidene fluoride (70%)-tetrafluoroethylene (30%) copolymer(P(VDF-TrFE), referred to herein as PVT). The molecular structure 200 ofPVT is shown in FIG. 2. The polarization charge density of PVT is about100 mC/m², which arises from the large electron affinity differencebetween fluorine atoms 202 and hydrogen atoms 204 in the material. PVTis capable of retaining its ferroelectric polarization state even infilms as thin as approximately 1 nm. In addition, PVT is chemicallyinert, can be fabricated at low temperatures, is photostable, and iscompatible with polymer semiconductor materials, rendering it wellsuited for use in the photovoltaic device 100. Other materials havingdipoles and high polarization charge density may also be used for thedipole layer 118. In the examples described herein, the dipole layer 118is formed of PVT unless otherwise stated.

Referring again to FIG. 1, the photoactive layer 102 is disposed on asubstrate 104. The substrate 104 includes a transparent supportsubstrate 106, such as glass, and a transparent first electrode 108,such as indium tin oxide. In some examples, a transition layer 110 isformed between the substrate 104 and the photoactive layer 102. Thetransition layer 110 may be formed of, e.g.,Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). Asecond electrode 112 formed of a metal, such as aluminum or silver, isdisposed on the photoactive layer 102.

FIG. 3 is a flow diagram of an exemplary process for fabricating thephotovoltaic device 100. A cleaned substrate of indium tin oxide onglass was treated by ultraviolet-ozone for ten minutes (300).Poly(3,4-ethylenedioxythiophene):poly)styrenesulfonate) (PEDOT:PSS)(Baytron-P 4083, H.C. Starck, Goslar, Germany) was spin coated onto thetreated substrate at a spin speed of 3500 rpm (302). The resultingPEDOT:PSS film was approximately 30 nm thick, as measured with a Dektakprofilometer. The PEDOT:PSS film was baked at 125° C. for 30 minutes.

A 20 mg/mL solution of P3HT (Rieke, Lincoln, Nebr., used as received) in1,2-dichlorobenzene was spin coated onto the PEDOT:PSS film at a spinspeed of 1000 rpm for 25 seconds followed by a spin speed of 2000 rpmfor 35 seconds to form a donor layer of P3HT with a thickness of about80 nm (304). A dipole layer of PVT (70:30) (Kunshan Hisense ElectronicsCo., Ltd, China) was coated onto the P3HT donor layer byLangmuir-Blodgett deposition and annealed at 135° C. for 30 minutes(306). A 5 mg/mL solution of PCBM in dichloromethane was spin coatedonto the dipole layer and annealed at 140° C. for 20 minutes (308). Anupper cathode was fabricated by thermally evaporating 10 nm of calciumcovered by 100 nm of aluminum (310). The active device area was about0.07 cm². The values of various parameters used in the fabricationprocess described above are merely examples. The parameters can haveother values. Other thin film fabrication methods may also be used, suchas printing, mist coating, or other deposition processes.

Referring to FIG. 4A, in an organic semiconductor photovoltaic devicehaving a donor layer 114 and an acceptor layer 116, the relativepositions of the energy levels of the donor layer 114 and the acceptorlayer 116 affect the efficiency of the photovoltaic device.

The donor layer 114 and the acceptor layer 116 each have a lowestunoccupied molecular orbital (LUMO) 402, 404, respectively, and ahighest occupied molecular orbital (HOMO) 406, 408, respectively. Theoffset 410 between the LUMO 402 of the donor layer 114 and the LUMO 404of the acceptor layer 116 is referred to as the “LUMO offset.” Chargetransfer efficiency between the donor layer 114 and the acceptor layer116 is affected by the magnitude of the LUMO offset 410; charge transferis generally more efficient between materials having a small LUMO offset410.

In addition, the magnitude of the LUMO offset 410 is inversely relatedto the energy difference E_(DA) between the HOMO 406 of the donor layer114 and the LUMO 404 of the acceptor layer 116. The energy differenceE_(DA) in turn is substantially linearly correlated with the opencircuit voltage V_(OC) of the photovoltaic device. In general, aphotovoltaic device having a large open circuit voltage V_(oc) performsmore efficiently than a photovoltaic device having a small open circuitvoltage V_(oc). Thus, an efficient photovoltaic device generally has alarge open circuit voltage V_(oc), a large energy difference E_(DA), anda small LUMO offset 410.

In a structure 400 in which the donor layer 114 directly contacts theacceptor layer 116, the LUMO offset 410 is large, which results in asmall energy difference E_(DA) and a small open circuit voltage V_(oc1).

Referring to FIG. 4B, without being bound by theory, it is believed thatthe presence of the dipole layer 118 between the donor layer 114 and theacceptor layer 116 causes a shift in the energy levels of the layers. Inparticular, it is believed that the dipole layer 118 reduces the LUMOoffset 410, improving charge transfer efficiency between the donor layer114 and the acceptor layer 116. In addition, the reduction in LUMOoffset 410 causes an increase in the energy difference E_(DA) and theopen circuit voltage V_(oc2) of the photovoltaic device, which suggestsa higher efficiency the photovoltaic device.

In an organic photovoltaic device, efficient photoinduced chargetransfer between the donor layer 114 and the acceptor layer 116 isrelevant to the efficiency of the device. The presence of the dipolelayer 118 is believed to improve the efficiency of such charge transfer(e.g., by reducing the LUMO offset 410 between the donor layer 114 andthe acceptor layer 116). However, if the dipole layer 118 is too thick,the charge transfer efficiency across the dipole layer 118 may beadversely affected.

In some examples, the dipole layer 118 may be formed as thin as possibleto achieve a desired energy level shift without adversely affectingcharge transfer efficiency between the donor layer 114 and the acceptorlayer 116. For instance, in one approach, the minimum dipole layerthickness (d) sufficient to achieve a desired energy level shift (E) canbe estimated from the polarization charge density (σ_(P)) and thedielectric constant (∈_(d)) of the material of the dipole layer 118 asfollows:

$d = \frac{ɛ_{0}ɛ_{d}E}{\sigma_{P}q}$

where ∈₀ is the vacuum dielectric constant and q is the elementalelectron charge.

For example, for a dipole layer formed of PVT, a thickness of only about0.6 nm, which corresponds to about one monomolecular layer of PVT, iscapable of inducing an energy level shift of about 0.8 eV. This energylevel shift corresponds to a LUMO offset of about 0.2 eV, which may besufficient to improve the efficiency of charge transfer between thedonor layer 114 and the acceptor layer 116. A dipole layer 118 of suchthickness is likely to have little or no adverse effect on theefficiency of charge transfer by tunneling between the donor layer 114and the acceptor layer 116.

Photoluminescence measurements can characterize the effect of a thin PVTdipole layer on the efficiency of photoinduced charge transfer betweenthe donor layer 114 and the acceptor layer 116. Referring to FIG. 5,photoluminescence measurements were conducted on a single layer sampleof donor material (P3HT), a bilayer sample including the donor layer 114(P3HT) and the acceptor layer 116 (PCBM), and a trilayer sampleincluding the donor layer 114 (P3HT), a monolayer (about 0.6 nm thick)of the dipole layer 118 (PVT), and the acceptor layer 116 (PCBM).Photoluminescence measurements were conducted using a commercialspectrophotometer (F-4500, Hitachi Inc.) equipped with a standard solidsample holder. The excitation light was provided by a Xenon lamprestricted to a spectral window of 480±2.5 nm. The photoluminescenceemission from the sample was dispersed by a grating and thephotoluminescence spectra were recorded at a speed of 60 nm/minute usinga photomutiplier tube (R3788, Hamamatsu Photonics K.K., Bridgewater,N.J.) operated at 700 V.

The sample of donor material displayed a high photoluminescenceintensity (curve 504) that peaked at about 1.0. In the bilayer sample, adramatically lower photoluminescence intensity (curve 506) was observed,indicating the occurrence of charge transfer between the donor layer 114and the acceptor layer 116. In the trilayer sample including the dipolelayer 118, the photoluminescence intensity reduced further (curve 508).This result demonstrates that the presence of the dipole layer 118 doesnot hinder photoinduced charge transfer between the donor layer 114 andthe acceptor layer 116 and may even improve the charge transferefficiency. Without being bound by theory, it is believed that thedipole layer may improve charge transfer efficiency because the LUMOoffset is larger than the molecular reorganization energy. The systemthus enters the so-called “inverted” region of Marcus theory, resultingin an increased electron transfer rate.

Referring to FIG. 6, the current density was measured as a function ofvoltage for an as-fabricated (i.e., unpoled) P3HT-PCMB photovoltaicdevice including a PVT dipole layer (e.g., such as the device 100 shownin FIG. 1). The device exhibited a short circuit current density J_(sc)of 8.2 mA/cm² and an open circuit voltage V_(oc) of 0.55 V, as can beseen from curve 600. The fill factor and the power conversion efficiencyof the unpoled device were determined to be 33% and 1.5%, respectively.These values are typical for a bilayer organic photovoltaic device witha P3HT donor layer and a PCBM acceptor layer. Photocurrent was measuredunder simulated air mass 1.5 global irradiation (100 mW/cm²).

Upon application of a reverse bias voltage to the photovoltaic device,the dipoles in the dipole layer partially or completely align along thedirection of the applied field. A reverse bias voltage can be applied tothe photovoltaic device by, for example, connecting the electrodes 108and 112 to a voltage difference such that the voltage applied to theelectrode 108 is lower than the voltage applied to the electrode 112.Because of the ferroelectric nature of the dipole layer, the dipolesremained aligned even after removal of the bias voltage. The applicationand removal of a bias voltage to a photovoltaic device is referred toherein as “poling” the device. Referring still to FIG. 6, after reversepoling the photovoltaic device with a large reverse bias voltage (e.g.,−16 V), the photovoltaic device exhibited a higher short circuit currentdensity J_(sc) of about 9.0 mA/cm² and a higher open circuit voltageV_(oc) of 0.67 V, as can be seen from curve 602. The fill factor of thereverse poled device was increased to 55% and the power conversionefficiency more than doubled to 3.3% as compared with the unpoleddevice. It is thus apparent that the performance of an organicphotovoltaic device can be improved by the presence of a poled dipolelayer between the donor layer and the acceptor layer.

The polarization state of the dipole layer is bistable and can beswitched between opposite states by application of a voltage pulse ofthe appropriate polarity. This state switching enables the performanceof a photovoltaic device including a dipole layer to be tuned. Referringstill to FIG. 6, after forward poling the photovoltaic device with asmall forward bias voltage (e.g., +2V), the dipoles in the dipole layeralign in the opposite direction (compared to the situation where areverse bias voltage is applied). A forward bias voltage can be appliedto the photovoltaic device by, for example, connecting the electrodes108 and 112 to a voltage difference such that the voltage applied to theelectrode 108 is higher than the voltage applied to the electrode 112.The forward poled device still exhibited an improvement in performance(as can be seen from curve 604) as compared to the unpoled device, butthe improvement was less significant than the improvement resulting fromreverse poling. The +2 V forward bias applied in this example isrelatively small so as to avoid generating a high current density thatcould potentially burn the device. Thus, it is possible that the lesspronounced improvement in performance may be due to only partialalignment of the dipoles in the dipole layer.

Referring to FIG. 7, the dark current of the photovoltaic device canalso be tuned by poling the device. The dark current of an unpoleddevice including a dipole layer is shown in curve 700. After reversepoling (−16 V), the dark current is reduced by a factor of four, as canbe seen from curve 702. Forward poling (+2 V) causes a lesser reductionin the dark current of the device, as can be seen from curve 704.

Without being bound by theory, it is believed that the reduction in darkcurrent is due to the tuning of the energy levels of the donor andacceptor layers that results from the alignment of dipoles in the dipolelayer. In a bilayer organic photovoltaic device (i.e., a deviceincluding a donor layer and an acceptor layer but not a dipole layer),the dark current originates from thermal activation of electrons fromthe HOMO of the donor layer to the LUMO of the acceptor layer. Theactivation energy of this process is E_(DA), as can be seen from thegeneral expression for the open circuit voltage V_(oc) in an organicphotovoltaic device:

$V_{oc} = {{\frac{nkT}{q}{\ln \left( {\frac{J_{sc}}{J_{0}} + 1} \right)}} \approx {\frac{nkT}{q}{\ln \left( \frac{J_{sc}}{J_{0}} \right)}}}$${J_{0} = {J_{00}{\exp \left( \frac{- E_{DA}}{nkT} \right)}}},$

where k is the Boltzmann constant, T is temperature, q is the elementalelectron charge, J₀ is the saturated dark current density, J₀₀ is afactor for the recombination of charge transfer excitons (e.g., boundelectron-hole pairs), and n is the diode ideality factor.

As discussed above (e.g., as shown in FIGS. 4A and 4B), when a poleddipole layer is present between the donor layer and the acceptor layerof a photovoltaic device, the LUMO of the acceptor layer is shiftedupwards, causing E_(DA) to increase. According to the above equations,the increase in E_(DA) reduces the saturated dark current density J₀,thus increasing the open circuit voltage V_(oc) and resulting inimproved device performance. The presence of the dipole layer may alsoreduce the electronic coupling between the donor layer and the acceptorlayer by increasing the spacing between the layers, hence reducing therecombination of charge transfer excitons. This reduction inrecombination is reflected by a reduction in J₀₀, which results in afurther increase in the open circuit voltage V_(oc) and further improveddevice performance.

Piezoresponse force microscopy measurements were conducted tocharacterize the morphology and ferroelectric state of the dipole layer.Piezoresponse force microscopy is able to measure the localpiezoelectric response on the surface of a material as well as inunderlying layers of material. For instance, piezoresponse forcemicroscopy can measure the piezoelectric response of the dipole layerembedded under the acceptor layer and a thin layer of metal. Thepiezoelectric response of a material is related to the net electricpolarization of the material; thus, piezoresponse force microscopy canbe used to probe the local polarization state of the material. In theexamples below, a piezoresponse force microscope model MFP-3Dmanufactured by Asylum Research (Goleta, Calif.) was used.

FIGS. 8A and 8B are piezoresponse force microscopy amplitude and phaseimages, respectively, of nanoislands 800 of a dipole layer material(PVT) on the surface 802 of a donor layer (P3HT). The ferroelectricstate of the nanoislands 800, as indicated by the light color of thenanoislands in the images, suggests that the nanoislands are capable ofmaintaining permanent polarization. The nanoislands 800 coverapproximately 20% of the surface 802 of the donor layer. Without beingbound by theory, it is believed that PVT on a P3HT surface shrinks uponthermal annealing, resulting in incomplete surface coverage and theformation of the observed nanoislands 800.

The open circuit voltage V_(oc) of 0.67 V observed in the poledphotovoltaic device including a dipole layer is less than the maximumopen circuit voltage of 1.5 V that is theoretically attainable from aphotovoltaic device including a dipole layer. This difference may be dueto the morphology of the dipole layer and the presence of thenanoislands 800. The incomplete surface coverage of the dipole layer onthe donor layer surface causes direct contact between the donor layerand the acceptor layer. In such a structure, the observed open circuitvoltage can be considered to be the average open circuit voltage of manynanoscale organic photovoltaic devices connected in parallel, some ofwhich include a dipole layer (i.e., at the locations of the nanoislands800) and others of which do not include a dipole layer (i.e., where thedonor layer directly contacts the acceptor layer). By increasing thesurface coverage and uniformity of the dipole layer on the donor layer,the open circuit voltage may be further increased as the amount ofcontact between the donor layer and the acceptor layer is reduced.

The ferroelectric state of the nanoislands 800 was further probed byapplying a pulse voltage between the piezoresponse force microscopy tipand one nanoisland 800 to obtain a direct observation of thepolarization of the nanoisland. A topographic piezoresponse forcemicroscopy image of an example nanoisland 800 is shown in FIG. 9A.Forward and reverse biases were applied to the nanoisland 800 topolarize the dipoles in the nanoisland. Referring to FIG. 9B, phase 900and amplitude 902 hysteresis measurements were collected duringapplication of the biases. The hysteresis loops reveal that a reversecoercive bias of −2.6 V or a forward coercive bias of +3 V is sufficientto substantially completely polarize the dipoles in the nanoisland 800.Upon application of a reverse bias of −6 V, the polarization directionof the nanoisland 800 can be reversed, as can be seen from thepiezoresponse force microscopy phase images shown in FIG. 9C (beforepoling) and FIG. 9D (after poling).

Electrostatic force microscopy (EFM) was used to confirm the tuning ofthe relative energy levels between the donor layer and the acceptorlayer by the presence of the poled dipole layer. The substrate (e.g.,indium tin oxide) of a photovoltaic device including a dipole layer wasgrounded and a region of the device was poled by scanning a platinum tipacross the region in contact mode to apply a forward bias of +4 Vbetween the tip and the substrate in the scanned region. After polingthe device, a potential image of the substrate was measured innon-contact (e.g., tapping) mode with a small bias of +0.2 V on theplatinum tip. In the examples below, electrostatic force microscopy wasconducted using an EnviroScope Atomic Force Microscope (ESCOPE)manufactured by Veeco, Digital Instruments (Lowell, Mass.).

FIGS. 10A and 10B show topography 1000 and surface potential 1002electrostatic force microscopy images, respectively, of the photovoltaicdevice after forward poling. The region inside the dashed rectangle 1004indicates the region that was poled by the forward bias of +4 V. Thetopography of the device (FIG. 10A) was not changed by the poling of thedipole layer. The electrical potential (FIG. 10B) in the poled regiondropped by 100 mV and can be seen by the darker color inside the dashedrectangle 1004. Referring to FIG. 10C, this electrical potentialdifference can also be observed by viewing a cross sectional analysis ofthe electrical potential image of FIG. 10B along a line 1006 within theunpoled region and along a line 1008 within the poled region of thedevice.

The average surface potential difference of 0.1 V between poled andunpoled regions of the device is consistent with the change in the opencircuit voltage of the photovoltaic device measured above. Thefluctuation of the surface potential (peak to valley potentialdifference of at least about 0.3 V) is consistent with the nonuniformdistribution of the dipole layer on the donor layer surface (e.g., thepresence of nanoislands). Referring to FIG. 11, without being bound bytheory, it is believed that the difference in surface potential betweenpoled and unpoled regions of the device may be due to the alignment ofthe electrical dipoles in the poled region. In the unpoled region (top),dipoles 1100 in the dipole layer are not aligned. In the poled region(bottom), the dipoles 1100 are substantially aligned according to thedirection of the applied bias, resulting in the generation of a surfaceelectric field.

The surface electric field generated by the aligned dipoles in thedipole layer causes a shift in the energy levels of the donor layer andthe acceptor layer in a photovoltaic device, resulting in an increase inthe open circuit voltage V_(oc) and an improved power conversionefficiency of the device.

Although the examples described above characterized a photovoltaicdevice formed with P3HT:PCMB and with a dipole layer of PVT, othermaterials are also possible. For instance, other organic semiconductorsmay be used for the donor layer, the acceptor layer, or both, in orderto achieve a desired performance. Other materials may also be used forthe dipole layer, such as materials that include polarizable dipolesthat are capable of maintaining polarization after removal of apolarizing external electric field.

Referring to FIG. 12, in another embodiment, an organic Schottkyjunction photovoltaic device 1200 includes a single active layer 1202disposed on a transparent, conductive substrate 1204, such as indium tinoxide on glass. In some examples, an anode layer 1206 is present betweenthe substrate 1204 and the active layer 1202 to form a Schottky junction1205. A cathode layer 1208 is formed over the active layer 1202 to forman Ohmic contact.

The anode layer 1206 may be made of any appropriate material orcombination of materials that, in conjunction with the active layer1202, is capable of forming a Schottky junction. For example, the anodelayer 1206 may be formed of one or more of the following materials:indium-tin oxide (ITO), indium-zinc oxide, silver, gold, platinum,copper, chromium, indium oxide, zinc oxide, tin oxide, a polyaniline(PANI)-based conducting polymer, a3,4-polyethylenedioxythiopene-polystyrenesultonate (PEDOT)-basedconducting polymer such as PEDOT:PSS, carbon nanotubes (CNT), graphite,graphene, molybdenum oxide (MoOx), tungsten oxide, vanadium oxide,silver oxide, aluminum oxide, or combinations thereof.

The top cathode layer 1208 may be made of any appropriate material orcombination of materials that, in conjunction with acceptor material inthe active layer 1202, results in ohmic contact at the interface betweenthe active layer and cathode. For example, the cathode may be formed ofone or more of the following materials: an alkali metal (e.g., lithium,sodium, potassium, or cesium), an alkaline earth metal (e.g., magnesium,calcium, strontium, or barium), a transition metal (e.g., chromium,iron, cobalt, nickel, copper, silver, gold, or zinc), a lanthanoid(e.g., samarium or ytterbium), tin, aluminum, a transition metal oxide(e.g., zinc oxide or titanium oxide), an alkali metal fluoride (e.g.,lithium fluoride), an alkaline earth metal fluoride, an alkali metalchloride, an alkaline earth metal chloride, an alkali metal oxide, analkaline earth metal oxide, a metal carbonate, a metal acetate,graphene, bathocuproine (BCP), phenanthroline and derivatives thereof(e.g., bathophenanthroline (BPhen)), or combinations thereof.

In some examples, the active layer 1202 is formed of a fullerene-basedacceptor material, such as [6,6]-phenyl-C71 butyric acid methyl ester(PC70BM), with a small percentage (e.g., 5% by weight) of a donormaterial, such as P3HT. Referring to FIGS. 13A and 13B, a photovoltaicdevice 1200 formed with such an active layer exhibited a short circuitcurrent density J_(sc) of 8.65 mA/cm² and an open circuit voltage V_(oc)of 0.868 V, as can be seen from curve 1300. The fill factor of thedevice was 44% and the power conversion efficiency was 3.3% under anillumination of 100 mW/cm². The open circuit voltage of this device 1200is larger than the open circuit voltage for a typical bulkheterojunction device formed with an active layer including only anacceptor material. However, the fill factor for this device isrelatively low, which may be due to the charge recombination that occursin fullerene-based films.

In some examples, a dipole material, such as PVT (e.g., 10% by weight)is also added to the active layer 1202, forming an active layer thatcontains acceptor material, donor material, and dipole material.

Before poling, a photovoltaic device 1200 formed with an active layerincluding a dipole material exhibited a short circuit current densityJ_(sc) and an open circuit voltage V_(oc) of 9.08 mA/cm² and 0.850 V,respectively, as can be seen from curve 1302. The fill factor and powerconversion efficiency were enhanced to 45% and 3.5%, respectively, ascompared to the device without dipole material. This performanceenhancement may be explained by the increase in the dielectric constantof the active layer 1202 caused by the addition of the dipole material,which in turn leads to a reduction in the Coulombic attraction of chargetransfer excitons generated in the active layer 1202.

After poling by applying a reverse bias of −6 V to the photovoltaicdevice 1200 formed with an active layer 1202 including a dipolematerial, the device efficiency was increased by 12%. Specifically, thedevice exhibited a short circuit current density J_(sc) and an opencircuit voltage V_(oc) of 8.92 mA/cm² and 0.875 V, respectively, as canbe seen from curve 1304. The fill factor and power conversion efficiencywere 47% and 3.7%, respectively. This performance enhancement may beexplained by the alignment of dipoles in the dipole material, whichgenerates a barrier that impedes the recombination of charge transferexcitons in the active layer 1202.

The foregoing description is intended to illustrate and not to limit thescope of the invention, which is defined by the scope of the appendedclaims. Other embodiments are within the scope of the following claims.

1. An apparatus comprising: a substrate; and a photoactive layer disposed on the substrate, the photoactive layer comprising: an electron acceptor material; an electron donor material; and a material having dipoles, in which at least one of the electron acceptor material or the electron donor material is between the substrate and the material having dipoles.
 2. The apparatus of claim 1, wherein the electron acceptor material includes fullerenes.
 3. The apparatus of claim 1, wherein the dipoles align upon application of a bias electric field.
 4. The apparatus of claim 1, wherein the material having dipoles has a polarization charge density of at least about 5 mC/m².
 5. The apparatus of claim 1, wherein the material having dipoles is configured to cause a shift in an energy level of at least one of the electron acceptor material and the electron donor material.
 6. The apparatus of claim 6, wherein the dipoles reduce an offset between the lowest unoccupied molecular orbits of the electron acceptor material and the electron donor material.
 7. The apparatus of claim 1, wherein the material having dipoles comprises a ferroelectric polymer.
 8. The apparatus of claim 1, wherein the material having dipoles includes polyvinylidene fluoride and tetrafluoroethylene.
 9. The apparatus of claim 1, wherein the material having dipoles comprises liquid crystal molecules.
 10. The apparatus of claim 1, wherein at least one of the electron acceptor material and the electron donor material comprises an organic semiconductor material.
 11. An apparatus comprising: an electrically conductive substrate; a photoactive layer disposed on the substrate, the photoactive layer comprising: an electron acceptor material; an electron donor material; and a material having dipoles, in which at least one of the electron acceptor material or the electron donor material is between the substrate and the material having dipoles; and an electrical contact disposed on the photoactive layer.
 12. The apparatus of claim 11, wherein the material having dipoles is configured to increase an open circuit voltage between the substrate and the electrical contact.
 13. The apparatus of claim 11, wherein the material having dipoles is configured to cause a shift in an energy level of at least one of the electron acceptor material and the electron donor material
 14. The apparatus of claim 11, wherein the dipoles align upon application of a bias to the polarizable material.
 15. The apparatus of claim 11, wherein the substrate is transparent.
 16. The apparatus of claim 11, wherein at least one of the electron acceptor material and the electron donor material comprises an organic semiconductor material.
 17. A method comprising: forming a photoactive layer on an electrically conductive substrate, the photoactive layer comprising: an electron acceptor material; an electron donor material; and a material having dipoles, in which at least one of the electron acceptor material or the electron donor material is between the substrate and the material having dipoles; forming an electrical contact on the photoactive layer; and applying an electrical bias to the material having dipoles.
 18. The method of claim 17, wherein applying an electrical bias to the material having dipoles includes causing dipoles to align.
 19. The method of claim 17, wherein applying an electrical bias to the material having dipoles includes causing an increase in an open circuit voltage between the substrate and the electrical contact.
 20. The method of claim 17, wherein at least one of the electron acceptor material and the electron donor material is an organic semiconductor material.
 21. The apparatus of claim 1, wherein the substrate includes a layer of a conductive material disposed on a support substrate.
 22. An apparatus comprising: a substrate; and a photoactive layer disposed on the substrate, the photoactive layer comprising: an electron acceptor material; an electron donor material; and a material having dipoles, in which the material having dipoles is between the electron acceptor material and the electron donor material.
 23. The apparatus of claim 22, wherein the dipoles align upon application of a bias to the photoactive layer.
 24. The apparatus of claim 22, wherein at least one of the electron acceptor material and the electron donor material is an organic semiconductor material.
 25. The apparatus of claim 22, wherein the substrate is transparent.
 26. The apparatus of claim 22, wherein the material having dipoles comprises a ferroelectric polymer.
 27. The apparatus of claim 22, wherein the material having dipoles comprises liquid crystal molecules. 